Oxocarbon-, pseudooxocarbon- and radialene compounds and their use

ABSTRACT

The present invention relates to oxocarbon-, pseudooxocarbon- and radialene compounds as well as to their use as doping agent for doping an organic semiconductive matrix material, as blocker material, as charge injection layer, as electrode material as well as organic semiconductor, as well as electronic components and organic semiconductive materials using them.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.15/817,398, filed Nov. 20, 2017, which is a divisional of U.S. patentapplication Ser. No. 14/570,443, filed Dec. 15, 2014, now U.S. Pat. No.9,876,172, which is a divisional of U.S. patent application Ser. No.14/080,340, filed Nov. 14, 2013, now U.S. Pat. No. 8,911,645, which is adivisional of U.S. patent application Ser. No. 13/178,855, filed Jul. 8,2011, now U.S. Pat. No. 8,617,426, which is a divisional of U.S. patentapplication Ser. No. 12/111,326, filed Apr. 29, 2008, now U.S. Pat. No.7,981,324, which claims foreign priority to European Patent ApplicationNo. 07008747.3, filed Apr. 30, 2007. Each of these applications isincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to oxocarbon-, pseudooxocarbon- andradialene compounds as well as to their use as organic doping agent fordoping an organic semiconductive matrix material for changing itselectrical properties, as blocker material as well as charge injectionlayer and as electrode material. The invention also relates to organicsemiconductive materials as well as to electronic components in whichthe oxocarbon-, pseudooxocarbon- and radialene compounds are used.

In the present application alicyclics in which all ring atoms aresp2-hybridized and to the extent possible carry exocyclic C—C doublebonds are designated as radialenes, see also H. Hopf and G. Maas, Angew.Chem. (1992), 8, 955. Oxocarbon- and pseudooxocarbon compounds aresufficiently known as non-benzoid aromatics, see, e.g., G. Seitz, Nachr.Chem. Tech. Lab. 28 (1980), pages 804-807. The first oxocarbon compound,potassium croconate, was produced by L. Gmelin in 1825 from potash andcoal. Those compounds, in which at least one oxygen atom is replaced byanother heteroatom, are designated as pseudooxocarbons, as is readilyknown to an expert in the art.

It has been known for several years that organic semiconductors can beheavily influenced regarding their electrical conductivity by doping.Such organic semiconductive matrix materials can be built up either fromcompounds with good electron donor properties or from compounds withgood electron acceptor properties. Strong electron acceptors such astetracyanoquinonedimethane (TCNQ) or2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4TCNQ) havebecome known for the doping of electron donor materials (HT), M.Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22),3202-3204 (1998). and J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl.Phys. Lett., 73 (6), 729-731 (1998). They generate so-called holes byelectron transfer processes in electron donor-like base materials (holetransport materials) by the number and mobility of which holes theconductivity of the base material is more or less significantly changed.For example, N,N′-perarylated benzidines TPD or N,N′,N″-perarylatedstarburst compounds such as the substance TDATA, or, however, alsocertain metal phthalocyanines, such as in particular zinc phthalocyanineZnPc are known as matrix material with hole transport properties.

However, the previously described compounds have disadvantages for atechnical use in the production of doped semiconductive organic layersor of corresponding electronic components with such doped layers sincethe manufacturing processes in large-scale production plants or those ona technical scale can not always be sufficiently precise, which resultsin high control- and regulating expense within the processes forachieving a desired product quality or in undesired tolerances of theproducts. Furthermore, there are disadvantages in the use of previouslyknown organic donors with regard to electronic components such aslight-emitting diodes (OLEDs), field effect transistors (FET) or solarcells themselves since the cited production difficulties in the handlingof the doping agents can lead to undesired irregularities in theelectronic components or in undesired ageing effects of the electroniccomponents. However, it should be considered at the same time that thedoping agents to be used have extremely high electron affinities(reduction potentials) and other properties suitable for the applicationcase since, e.g., the doping agents also co-determine the conductivityor other electrical properties of the organic semiconductive layer undergiven conditions. The energetic positions of the HOMO of the matrixmaterial and of the LUMO of the doping agent are decisive for the dopingeffect.

The present invention has the task of overcoming the disadvantages ofthe state of the art, in particular to make new organic mesomericcompounds available that can be used in particular as doping agent forthe doping of organic semiconductors, that can furthermore be morereadily handled in the production process and that result in electroniccomponents whose organic semiconductive materials can be reproduciblymanufactured

This task is solved, at least in part, by the following organicmesomeric compound and/or the use of the organic mesomeric compound asorganic doping agent for the doping of an organic semiconductive matrixmaterial, as blocker layer, as charge injection layer or as organicsemiconductor itself, characterized in that the mesomeric compound is anoxocarbon-, pseudooxocarbon- or radialene compound with the followingformula:

in which n=1-4; each X₁, X₂, X₃, X₄, and X₅ is independently selectedfrom the group consisting of C(CN)₂, (CF₃)C(CN), (NO₂)C(CN),C(halogen)₂, C(CF₃)₂, NCN, O, S, NR₁,

in which Y=CN, NO₂, COR₁ or is perhalogenated alkyl; aryl or Ar is asubstituted or unsubstituted, aromatic hydrocarbon or biaryl, optionallypolycyclic; hetaryl is a substituted or unsubstituted aromaticheterocyclic compound or biheteroaryl, preferably electron-poor,optionally polynuclear or partially or completely hydrogenated orfluorinated; and R₁-R₈ are independently selected from hydrogen,halogen, CN, NO₂, COR₁, alkyl, alkoxy, aryl and heteroaryl. In oneembodiment, Y is perfluoroalkyl, including, for example, CF₃. In anotherembodiment, aryl or Ar is partially or completely hydrogenated, orpartially or completely fluorinated. In a further embodiment, hetaryl isselected from pyridyl, pyrimidyl, triazine, or oxadizole. In a stillfurther embodiment, R1-R8 are independently selected from perhalogenatedand/or partially halogenated alkyl groups, including, for example,perfluorinated alkyl groups.

DETAILED DESCRIPTION

In the compounds in accordance with the invention the position of theLUMO is so low that further technically interesting hole transportmaterials can now be efficiently doped for the first time. Due to theextremely low position of the LUMO and to the associated high reductionpotential of the compounds even performance efficiencies of solar cellscan be significantly improved. In addition, these compounds areextremely diffusion-stable in organic layers on account of their highpolarity. The production processes can be better controlled and thus becarried out with lesser expense and in a more reproducible manner byhigher evaporation temperature and lower volatility under the sameconditions, whereby, by making available oxocarbons, pseudooxocarbonsand radialenes as doping agents, these make possible a sufficientelectrical conductivity of the organic semiconductive matrix givenadvantageous electron affinity of the doping agents in the particularcomponents at low diffusion coefficients that ensure a componentstructure that is uniform in time. Furthermore, the charge carrierinjection of contacts into the doped layer can be improved by the dopingagents. Furthermore, the doped organic semiconductive material and theresulting electronic component can have an improved long-time stabilityon account of the compounds used in accordance with the invention. Thisconcerns, e.g., a reduction of the doping concentration over time. Thisfurthermore concerns the stability of the doped layer that is arrangedadjacent to non-doped layers of an electro-optical component so thatelectro-optical components with increased long-time stability of theelectro-optical properties such as light yield at a given length,effectiveness of a solar cell or the like result.

The evaporation rate of a substrate with the compound used in accordancewith the invention can be determined, e.g., using a quartz thicknessmonitor, as is customarily used, e.g., in the production of OLEDs. Inparticular, the ratio of the evaporation rates of matrix materials anddoping agent can be measured by independent measurements of them usingtwo separate quartz thickness monitors in order to adjust the dopingratio.

It is understood that the compounds used in accordance with theinvention are preferably such that they evaporate more or less orpractically non-decomposed. However, if necessary, even purposefulprecursors can be used as doping source that release the compounds usedin accordance with the invention, e.g., acid addition salts, e.g., of avolatile or non-volatile inorganic or organic acid, or their chargetransfer complexes, which acids and/or electron donors are preferablynot volatile or only slightly volatile or the charge transfer complexitself acts as doping agent.

The doping agent is preferably selected in such a manner that itgenerates a conductivity just as high as or preferably higher thanF4TCNQ under conditions that are otherwise the same such as, inparticular, doping concentration (molar ratio, doping agent:matrix,layer thickness, current strength) at a given matrix material (e.g.,zinc phthalocyanine or another matrix material cited further below),e.g., a conductivity (s/cm) greater than/equal to 1.1 times, 1.2 timesor greater than/equal to 1.5 times or twice that of F4TCNQ as dopingagent.

The doping agent used in accordance with the invention is preferablyselected in such a manner that the semiconductive organic material dopedwith it still has ≥20%, preferably ≥30%, especially preferably ≥50% or60% of the conductivity (s/cm) of the value at 100° C. after atemperature change of 100° C. to RT (20° C.).

A few preferred oxocarbons, pseudooxocarbons and radialenes will beshown in the following that can be used with advantage for the purposesof the invention:

Further derivatives of oxocarbon-, pseudooxocarbon- and [6] radialenestructures

Preparation of the Oxocarbon-, Pseudooxocarbon- and Radialene Structures

The first oxocarbon compound, potassium croconate, was produced by L.Gmelin in 1825 from potash and coal. Oxocarbons and their esters andhalogenides preferably react with electron-rich compounds such asaliphatic and aromatic amines, aromatics and heteroaromatics. A. H.Schmidt, Synthesis (1980) 961. The reaction products fromtetrachlorocyclopropene and phenols in the presence of Lewis acids orCH-acidic compounds by strong bases, such as, e.g., arylacetonitriles,1,3-diketones, cyclopentadienes, malonodinitriles, acceptor-substituteddiarylmethanes, electron-poor diheteroarylmethanes are especiallysuitable for applications in accordance with the invention. [3]Radialenes are obtained after oxidation has taken place, R. West et al.J. Org. Chem. (1975) 40 2295; T. Kazuka, T. Shinji J. Chem. Soc. Chem.Commun. (1994) 519; T. Fukunaga et al. JACS (1976) 98 610.

Squaric acid dichloride and phenols, that can subsequently be oxidizedto 4 [radialenes] are furthermore also very well-suited, R. West, S. K.Koster J. Org. Chem. (1975) 40 2300; the nucleophilic anion of theCH-acidic melonic acid dinitrile can also be substituted with preferencewith esters under the splitting off of alcohol to dianionic squaric acidcompounds, T. Fukanaga J. Am. Chem. Soc. (1976) 98 610; W. Ziegenbein,H.-E. Sprenger Angew. Chem. (1967) 79 581; G. Seitz et al. Chem. Ber.(1987) 120 1691. The oxidation of these CN-substituted compounds wassuccessful only electrochemically in the past, T. A. Blinka, R. West,Tetrahedron Lett. (1983) 24 1567. [4]Radialenes can also be prepared bythermal dimerization of diquinone ethylenes, R. West, S. K. Koster, JOC(1975) 40 2300.

The first croconic acid derivatives that were substituted withmalodinitrile were able to be produced by Fatiadi, J. Org. Chem. (1980)45 1338, J. Am. Chem. Soc. (1978) 100 2586. The oxidation of thesecompounds was also examined electrochemically by him, A. J. Fatiadi, L.M. Doane, J. Electroanal. Chem. (1982) 135 193-209.

However, even [6] radialenes are known, H. Hopf, A. K. Wick Helv. Chim.Acta (1961) 46 380-6.

A few later representatives were and/or are used in theelectrophotography as electroluminescent material in video screens, asdye, as photoconductors, as organic oxidants, U.S. Pat. No. 4,003,943(1977), JP 07-168377, JP 2004010703 A (2004), U.S. Pat. No. 4,133,821(1979).

Preparation of New Cyclic Oxocarbon- and Pseudooxocarbon Derivatives

EXAMPLE a)1,3-Bis(dicyanomethylene)indane-2-ylidene-bis(4-oxo-[3,5-di-t-butyl]-2,-5-cyclohexadienylidene)-cyclopropane

4.75 g bis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienyl)-cyclopropenone,3,5 g 1,3-bis(dicyanomethylene)-indane as well as 60 mg β-alanine aredissolved in 12 ml acetic anhydride and briefly heated on the refluxunder stirring. The mixture is compounded with 60 ml toluene, allowed tocool off and the reddish-brown crystalline solid removed by suction. Themixture is subsequently washed with benzene/toluene and recrystallized.

Yield: 4.6 g

2.5 g of the reddish-brown crystals are dissolved under argon in 100 mlchloroform and united with a solution of 4.7 g red potassiumferrocyanide and 8.8 g KOH in 150 ml water. After 1 h intensivestirring, the organic phase is dried with Na2SO4 and evaporated to lowbulk and the product recrystallized.

Yield: 2.3 g blackish-green crystals fp. >250° C. under decomposition

b)(2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-pentafluor-ophenylacetonitrile)

A solution of 4 g (20 mmol) pentafluorophenylacetonitrile in 10 ml glymeare added dropwise to 1.6 g NaH in 40 ml glyme and cooled with icewater. Subsequently a solution of 0.9 tetrachloro cyclopropene in 10 mlglyme was added dropwise. After stirring for 24 h at room temperaturethe dark mixture is poured onto ice water and is extracted with CHCl₃.The extracts provide a black solid.

4 g of the raw intermediate product are dissolved in 50 ml CHCl₃, and tothis solution 50 ml water, containing 2 g K₂CO₃, is added. 0.5 mlbromine is added to this dark green 2-phase mixture under stirring.Thereafter, the phases are separated, and the organic phase isevaporated after drying over Na₂SO₄ using a rotatory evaporator. Aremaining orange solid is recrystallized using a suitable solvent.Yield: about 70%.

FP: 182° C.

c)(2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-[2′,3′,5′,-6′-tetrafluoropyrid-4′-yl]acetonitrile)

4.75 g 2,3,5,6-tetrafluoropyridyl actonitile in 10 ml glyme is addeddropwise to 0.4 g LiH in 60 ml glyme. Thereafter 1.1 gtetrachlorocyclopropene is added dropwise to the solution and is stirredover night. The mixture is poured onto ice-water and is extracted withEtOAc. After drying the extracts and evaporation 4.6 g of a solidremained.

2.25 g of the solid is dissolved in 50 ml AcOH, and 5 ml HNO₃ (65%) isadded. Water is added to this orange-brown solution, and the precipitateobtained is isolated, washed with water and dried. Yield: 1 g. Fp: 170°C.

d)(2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(2,6-dichloro-3,5-difluoro-4-(trisfluoromethyl)phenyl)acetonitrile)

0.29 g LiH are suspended in 68 ml glyme, and cooled, and 5 g2,6-dichloro-3,5-difluoro-4-(trifluoromethyl)phenyl)acetonitrile) in 6ml glyme are added slowly under argon atmosphere. The mixture is heatedto room temperature, and 0.8 g tetrachlorocyclopropene are addeddropwise, and the mixture is stirred over night. The solution is pouredonto ice-water, the precipitate obtained is isolated and dried. Yield:4.75 g.

3.5 g of the product is dissolved in glacial acetic acid, and undercooling 7 ml HNO₃ is dropwise added, subsequently water is added, andthe precipitate obtained is isolated. The product is recrystallizedutilizing a suitable solvent. Yield: 72%. Fp.: 185° C.

e)(2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(2,3,5,6-tetrafluoro-4-cyano-phenylacetonitrile)(2-2,3,5,6-tetrafluoro-4-trifluoromethyl-phenylacetonitrile)

Internal salt:2,3-bis(cyano(4-cyano-2,3,5,6-tetrafluorophenyl)methyl)-1-triethylamino)cycloprop-2-ene-1-ide.

5.34 g tetrachlorocyclopropene and 13.8 g2,3,5,6-tetrafluoro-4-cyanobenzylcyanid in 300 ml CH₂Cl₂ are cooled, and17.1 g triethylamine is added. The resultant product is stirred andheated to room temperature. Then water is added, and the yellow solidobtained is removed, washed and dried at air. Yield: 93%.

1.15 g 2,3,5,6-tetrafluoro-4-(trifluoromethyl)-benzylcyanid in 15 ml THFis dropwise added to 0.46 g LDA in 55 ml THF. The solution is cooled,and a suspension of 2 g of the internal salt in DMPU is added dropwise.The solution is poured into ice-water. The precipitate is removed andwashed with water and subsequently dried in vacuo. Yield: 100%.

2.7 g of the material to be oxidized is dissolved in 70 ml AcOH, and 5.5ml HNO₃ (65%) is added dropwise. The material to be oxidized is thenprecipitated with water. After isolation, washing with water and dryingin vacuo the product is obtained in a yield of 90%. Fp: >250° C.

f)(2E,2′E,2″E,2′″E)-2,2′,2″,2′″-(cyclopropane-1,2,3,4-tetraylidene)tetrakis(2-2′,3′,5′,6′-tetrafluoro-4′-cyanophenyl)acetonitrile

1.2 g 1,2-bis-tosyl-3,4-bis-dimethylamino-quadratat is heated with 2.14g 2,3,5,6-tetrafluoro-4-cyano-benzylcyanid in 20 ml pyridin for 16 hwith stirring. The solution is concentrated and given into ice-water.Thereafter it is extracted with EtOAc. Concentrating the dried extractsresults in the product which can be recrystallized in a suitablesolvent. Fp.: >250° C.

Matrix Materials

The present invention describes suitable doping agents for organicsemiconductive materials such as hole transport materials HT that arecustomarily used in OLEDs or organic solar cells. The semiconductivematerials are preferably intrinsically hole-conducting. The followingcan apply to doping agents of the oxocarbon- and pseudooxocarbon typesin accordance with the invention.

The matrix material can consist partially (>10 or >25% by weight) orsubstantially (>50% by weight or >75% by weight) or totally of a metalphthalocyanine complex, a porphyrine complex, especially metalporphyrine complex, oligothiophene-, oligophenyl-, oligophenylenevinylene- or oligofluorene compound, in which the oligomer preferablycomprises 2-500 or more, preferably 2-100 or 2-50 or 2-10 or moremonomeric units. The oligomer can also comprise >4, >6 or >10 or moremonomeric units, in particular also for the above-indicated ranges,thus, e.g., 4 or 6-10 monomeric units, 6 or 10-100 monomeric units or10-500 monomeric units. The monomers and oligomers can be substituted orunsubstituted and even block- or mixed polymerizates of the citedoligomers can be present as well as a compound with a triarylamine unitor a spiro-bifluorene compound. The cited matrix materials can also bepresent in combination with each other, optionally also in combinationwith other matrix materials. The matrix materials can haveelectron-donating substitutents such as alkyl- or alkoxy groups thathave a reduced ionizing energy or reduce the ionizing energy of thematrix material.

The metal phthalocyanine complexes or porphyrine complexes used asmatrix material can have a main group metal atom or subgroup metal atom.The metal atom Me can be coordinated 4-, 5- or 6-fold, e.g., in the formof oxo-(Me=O), dioxo-(O=Me=O) imine-, diimine-, hydroxo-, dihydroxo-,amino- or diamino complexes, without being limited to them. Thephthalocyanine complex or porphyrine complex can each be partiallyhydrogenated, however, the mesomeric ring system is preferably notdisturbed. The phthalocyanine can contain, e.g., magnesium, zinc, iron,nickel, cobalt, magnesium, copper or vanadyl (=VO) as central atom. Thesame or other metal atoms or oxometal atoms can be present in the caseof porphyrine complexes.

In particular, such dopable hole transport materials HT can be arylatedbenzidines, e.g., N,N′-perarylated benzidines or other diamines such asof the type TPD (in which one, several or all of the aryl groups canhave aromatic heteroatoms), suitable arylated starburst compounds suchas N,N′,N″-perarylated starburst compounds such as the compound TDATA(in which one, several or all of the aryl groups can have aromaticheteroatoms). The aryl groups can comprise phenyl, naphthyl, pyridine,quinoline, isoquinoline, peridazine, pyrimidine, pyrazine, pyrazole,imidazole, oxazole, furan, pyrrole, indole or the like, especially foreach of the above-cited compounds. The phenyl groups of the particularcompounds can be partially or completely replaced by thiophene groups.

The material used preferably consists completely of a metalphthalocyanine complex, a porphyrine complex, a compound with atriarylamine unit or a spiro-bifluorene compound.

It is understood that even other suitable organic matrix materials, inparticular hole-conducting materials can be used that havesemiconductive properties.

Doping

The doping can take place in particular in such a manner that the molarratio of matrix molecule to doping agent, or in the case of oligomericmatrix materials the ratio of matrix monomer number to doping agent is1:100000, preferably 1:10000, especially preferably 1:1 to 1:100000,e.g., 1:5 to 1:1000, e.g., 1:10 to 1:100, e.g., ca. 1:50 to 1:100 oralso 1:25 to 1:50.

Evaporation of the Doping Agents

The doping of the particular matrix material (preferably indicated hereas hole-conducting matrix material HT) with the doping agents to be usedin accordance with the invention can be produced by one or a combinationof the following processes:

a) Mixed evaporation in the vacuum with a source for HT and one for thedoping agent.

b) Sequential deposition of HT and doping agent with subsequent inwarddiffusion of the doping agent by thermal treatment

c) Doping of an HT layer by a solution of doping agent with subsequentevaporation of the solvent by thermal treatment

d) Surface doping of an HT layer by a layer of doping agent applied onthe surface.

The doping can take place in such a manner that the doping agent isevaporated out of a precursor compound that releases the doping agentunder heating and/or irradiation. The irradiation can take place byelectromagnetic radiation, especially visible light, UV light or IRlight, e.g., by laser light or also by other radiation types. The heatnecessary for evaporation can substantially be made available by theirradiation and can also be radiated in a purposeful manner into certainbands of the compounds or precursors or compound complexes such ascharge transfer complexes to be evaporated in order to facilitate theevaporation of the compounds by dissociation of the complexes byconversion into excited states. It is understood that the evaporationconditions described in the following are directed to those withoutirradiation and that uniform evaporation conditions are to be used forpurposes of comparison.

For example, the following can be used as precursor compounds:

a) Mixtures or stoichiometric or mixed crystalline compounds of thedoping agent and an inert, non-volatile substance, e.g., a polymer,molecular sieve, aluminum oxide, silica gel, and oligomers or anotherorganic or inorganic substance with high evaporation temperature, inwhich the doping agent is bound primarily by van der Waals forces and/orhydrogen bridge bonding to this substance.b) Mixture or stoichiometric or mixed crystalline compound of the dopingagent and one non-volatile compound V more or less of the electron donortype, in which a more or less complete charge transfer occurs betweenthe doping agent and the compound V as in charge transfer complexes withmore or less electron-rich polyaromatics or heteroaromatics or anotherorganic or inorganic substance with high evaporation temperature.c) Mixture or stoichiometric or mixed crystalline compound of the dopingagent and a substance that evaporates together with the doping agent andhas the same or higher ionizing energy as the substance HT to be doped,so that the substance does not form a trap for holes in the organicmatrix material. According to the invention the substance can also beidentical to the matrix material here, e.g., be a metal phthalocyanineor benzidine derivative. Further suitable volatile co-substances such ashydroquinones, 1,4-phenylene diamines or 1-amino-4-hydroxybenzene orother compounds form quinhydrones or other charge transfer complexes.Electronic Component

A plurality of electronic components or equipment containing them can beproduced using the organic compounds in accordance with the inventionfor producing doped organic semiconductive materials that can bearranged in particular in the form of layers or electrical line paths.In particular, the doping agents in accordance with the invention can beused to produce organic, light-emitting diodes (OLED), organic solarcells, organic diodes, especially those with a high rectification ratiosuch as 10³-10⁷, preferably 10⁴-10⁷ or 10⁵-10⁷ or organic field effecttransistors. The conductivity of the doped layers and/or the improvementof the charge carrier injection of contacts into the doped layer can beimproved by the doping agents in accordance with the invention. Inparticular in the case of OLEDs the component can have a pin structureor an inverse structure without being limited to them. However, the useof the doping agents in accordance with the invention is not limited tothe advantageous exemplary embodiments cited above.

EXEMPLARY EMBODIMENTS

The invention will be explained in detail with a few exemplaryembodiments.

The compounds to be used in accordance with the invention, inparticular, the previously indicated exemplary compounds from thepreviously described substance class of the oxocarbon- and of thepseudooxocarbon compounds will now be used in the following manner asdoping agents for different hole conductors that for their part are usedfor constructing certain microelectronic or optoelectronic componentssuch as, e.g., an OLED. The doping agents can be evaporated at the sametime adjacent to one another with the hole transport materials of thematrix in the high vacuum (ca. 2×10⁻⁴ Pa) at elevated temperatures. Atypical substrate evaporation rate for the matrix material is 0.2 nm/s(density ca. 1.5 g/cm³). The evaporation rates for the doping agents canvary between 0.001 and 0.5 nm/s at the same assumed density inaccordance with the desired doping ratio.

In the following examples the current measurements were carried out overa current path of the doped HT material 1 mm long and ca. 0.5 mm wide at1V. under these conditions ZnPc conducts practically no electricalcurrent.

EXAMPLES Example 1

Doping of ZnPc withdicyanomethylenebis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienylidene)cyclo-propane

Conductivity: 1,5×10⁻⁵ s/cm

Example 2

Doping of spiro-TTP withdicyanomethylenebis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienylidene)cyclo-propane

Conductivity: 3, 6×10⁻⁷ s/cm

Example 3

Doping of ZnPC with1,3-bis(dicyanomethylene)indane-2-ylidene-bis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienylidene)cyclopropane

Conductivity: 5,8×10⁻⁶ s/cm

Example 4

Doping of spiro-TTP with1,3-bis(dicyanomethylene)indane-2-ylidene-bis(4-oxo-[3,5-di-t-butyl]-2,5-cyclohexadienylidene)cyclopropaneconductivity: 5×10⁻⁷ S/cm

Example 5

Doping of N⁴,N⁴-(biphenyl-4,4%-diyl)bis(N⁴,N⁴′,N⁴′-triphenylbiphen-yl-4,4′-diamine)with(2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triyliden)tris(2-pentafluoroph-enylacetonitrile10%. Conductivity: 3.21×10⁻⁶ S/cm

Example 6

Doping of spiro-TTP with(2E,2′E,2″E)-2,2′,2″-cyclopropane-1,2,3-triylidene)tris(2-pentafluoroph-enylacetonitrile)10%. Conductivity: 1.89×10⁻⁶ S/cm.

Example 7

Doping of 4,4′-bis(10,11-dihydro-5H-dibenzo[b,f]azepine-5-yl)biphenylwith(2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-pentafluorophenylacetonitrile)10%. Conductivity: 1.55×10⁻⁷ S/cm.

Example 8

Doping of spiro-TTP with(2E,2′E,2″E)-2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-[2′,3′,5′,6′-tetrafluoropyrid-4′-yl]acetonitrile) 5%. Conductivity: 4.35×10⁻⁵S/cm.

Example 9

Doping of a-NPD with(2E,2′E,2″E)-2,2′,2″-cyclopropane-1,2,3-triylidene)tris(2-[2′,3′,5′,6′-tetrafluoropyrid-4′-yl]acetonitrile)5%. Conductivity: 1.28×10⁻⁵ S/cm.

Example 10

Doping of ZnPc with(N,N′,N″,N′″-cyclobutane-1,2,3,4-tetraylidene)tetraaniline 5%.Conductivity: 1.3×10⁻⁶ S/cm.

Example 11

Doping of spiro-TTP with(2E,2′E,2″E,2′″E)-2,2′,2″,2′″-(cyclobutane-1,2,3,4-tetraylidene)N,N′,-N″,N′″-cyclobutane-1,2,3,4-tetraylidene)tetrakis(2-perfluorophenyl)acetonitrile)5%. Conductivity: 3.3×10⁻⁵ S/cm.

The features of the invention disclosed in the previous description andin the claims can be essential individually as well as in anycombination for the realization of the invention in its variousembodiments.

The invention claimed is:
 1. An electronic component with anelectronically functionally active region, wherein the electronicallyactive region comprises a charge injection layer which consists of atleast one oxocarbon, pseudo-oxocarbon, or radialene compound with thefollowing formula:

in which n=1-4; each X₁, X₂, and X₃ is respectively independentlyselected from the group consisting of C(CN)₂, (CF₃)C(CN), (NO₂)C(CN),C(halogen)₂, C(CF₃)₂, NCN, O, S, NR₁,

wherein X₄ and X₅ are respectively independently selected from the groupconsisting of C(CN)₂, (CF₃)C(CN), (NO₂)C(CN), C(halogen)₂, C(CF₃)₂ NCN,O, S, and NR₁, wherein Y=CN, NO₂, COR₁ or is perhalogenated alkyl; aryl,respectively Ar is a substituted or unsubstituted aromatic hydrocarbonor biaryl, or optionally polycyclic; hetaryl is a substituted orunsubstituted aromatic heterocyclic compound or biheteroaryl, optionallypolynucleic or partially or completely hydrated or fluorinated; andR₁-R₈ are independently selected from hydrogen, halogen, CN, NO₂, COR₁,alkyl, alkoxy, aryl, or heteroaryl.
 2. The electronic component asclaimed in claim 1, wherein Y is perfluoroalkyl.
 3. The electroniccomponent as claimed in claim 2, wherein the perfluoroalkyl is CF₃. 4.The electronic component as claimed in claim 1, wherein the aryl ispartially or completely fluorinated.
 5. The electronic component asclaimed in claim 1, wherein the hetaryl is selected from pyridyl,pyrimidyl, triazine, or oxadiazole.
 6. The electronic component asclaimed in claim 1, wherein R₁-R₈ are independently selected fromperhalogenated and/or partially halogenated alkyl groups.
 7. Theelectronic component as claimed in claim 6, wherein R₁-R₈ areindependently selected from perfluorinated alkyl groups.
 8. Theelectronic component as claimed in claim 1, in the form of an organiclight emitting diode, a photovoltaic cell, an organic solar cell, anorganic diode, or an organic field effect transistor.
 9. The electroniccomponent as claimed in claim 1, wherein hetaryl is the substituted orunsubstituted aromatic heterocyclic compound or biheteroaryl, andhetaryl is electron-deficient.